WO2014148297A1 - Mousse stratifiée - Google Patents

Mousse stratifiée Download PDF

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Publication number
WO2014148297A1
WO2014148297A1 PCT/JP2014/056201 JP2014056201W WO2014148297A1 WO 2014148297 A1 WO2014148297 A1 WO 2014148297A1 JP 2014056201 W JP2014056201 W JP 2014056201W WO 2014148297 A1 WO2014148297 A1 WO 2014148297A1
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WIPO (PCT)
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less
mass
foam
parts
adhesive layer
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PCT/JP2014/056201
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English (en)
Japanese (ja)
Inventor
佑紀 福田
崇行 岩瀬
健史 五十嵐
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日東電工株式会社
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Publication of WO2014148297A1 publication Critical patent/WO2014148297A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0014—Use of organic additives
    • C08J9/0023—Use of organic additives containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0014—Use of organic additives
    • C08J9/0028—Use of organic additives containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0014—Use of organic additives
    • C08J9/0033—Use of organic additives containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
    • C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
    • C08J9/102—Azo-compounds
    • C08J9/103—Azodicarbonamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/36—After-treatment
    • C08J9/365—Coating
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/26—Porous or cellular plastics
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
    • C08J2201/026—Crosslinking before of after foaming
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
    • C08J2201/03—Extrusion of the foamable blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2205/00—Foams characterised by their properties
    • C08J2205/06—Flexible foams
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2207/00—Foams characterised by their intended use
    • C08J2207/02—Adhesive
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2300/00—Characterised by the use of unspecified polymers
    • C08J2300/26—Elastomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/16—Ethene-propene or ethene-propene-diene copolymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature

Definitions

  • the present invention relates to a foam laminate.
  • the foaming laminated body used suitably as a sealing material of various industrial products.
  • EPDM foams obtained by foaming ethylene / propylene / diene rubber (hereinafter sometimes abbreviated as EPDM) are known as sealing materials for various industrial products.
  • Such a resin foam is disposed between one member to be sealed and the other member, and is then compressed through the member, so that the member is sealed with the resin foam.
  • the resin foam single layer alone has a problem that the water stoppage at the seal portion (compressed resin foam) is insufficient.
  • the pressure-sensitive adhesive layer on the surface of the water sealing material described in Patent Document 1 does not have a tack force. Therefore, when the member to be sealed is placed on the surface of the water-stop sealing material and sealed, temporary fixing cannot be performed, and thus there is a problem that workability is inferior.
  • An object of the present invention is to provide a foam laminate that has good water-stopping properties, can be temporarily fixed, and can reduce contamination of members.
  • a foam laminate of the present invention comprises a foam layer formed from a resin foam and a pressure-sensitive adhesive layer laminated on at least one surface of the foam layer.
  • the shear storage modulus at 25 ° C. is 1.5 ⁇ 10 5 Pa or more, the 50% compression load is 0.40 N / cm 2 or less, and water can be stopped after 24 hours in the U-shaped water-stopping test.
  • the compression ratio is 60% or less.
  • the content of sulfur atoms in the resin foam is 1000 ppm or less.
  • the foam laminate of the present invention the content ratio of sulfur S 8 calculated based on the measurement result of gel permeation chromatography, it is preferable to set 100ppm or less by weight.
  • the pressure-sensitive adhesive layer contains a synthetic rubber.
  • the foam laminate of the present invention it is preferable that the foam laminate has a thickness of 1 mm to 50 mm, and the pressure-sensitive adhesive layer has a thickness of 1 ⁇ m to 100 ⁇ m.
  • the foam laminate of the present invention comprises a foam layer formed from a resin foam and an adhesive layer laminated on at least one surface of the foam layer, and the shear storage elastic modulus at 25 ° C. of the adhesive layer is Since it is 1.5 ⁇ 10 5 Pa or more, it can be temporarily fixed. Moreover, a 50% compressive load is 0.40 N / cm ⁇ 2 > or less, and the compressibility which can stop water 24 hours after in a U-shaped water-stopping test is 60% or less. Therefore, it is excellent in water stop. Furthermore, since water can be stopped with a low compressive load, when the foam laminate is peeled off after being sealed to the member, a part of the foam laminate is prevented from remaining on the member, and the low contamination property is excellent. Therefore, there is no need to remove the remaining foamed laminate, and the workability is excellent.
  • FIG. 1A to 1E are process diagrams for explaining an embodiment of the method for producing a foam laminate of the present invention.
  • FIG. 1A is a process for preparing a foam layer
  • FIG. 1B is an undercoat on one surface of the foam layer.
  • 1C is a step of disposing the pressure-sensitive adhesive layer laminated substrate and the foam layer opposite to each other
  • FIG. 1D is a step of laminating the pressure-sensitive adhesive layer and the foam layer (undercoat layer)
  • FIG. The process of peeling a peeling base material from a foaming laminated body is shown.
  • the foam laminate of the present invention comprises a foam layer formed from a resin foam and an adhesive layer laminated on at least one surface of the foam layer, and is used as a sealing material.
  • the resin foam examples include foams such as polyolefin foam, urethane foam, and rubber foam.
  • polyolefin foam examples include foamed polyethylene and foamed polypropylene.
  • urethane foam examples include flexible urethane foam, rigid urethane foam, urethane-modified polyisocyanurate foam, and polyisocyanurate foam.
  • a rubber foam is preferable.
  • the rubber-based foam is obtained, for example, by foaming a rubber composition containing rubber, a foaming agent and a crosslinking agent.
  • Examples of such rubbers include olefin elastomers such as ethylene-propylene rubber (EPM) and ethylene-propylene-diene rubber (EPDM), such as styrene-butadiene rubber (SBR) and styrene-butadiene-styrene rubber (SBS).
  • EPM ethylene-propylene rubber
  • EPDM ethylene-propylene-diene rubber
  • SBR styrene-butadiene rubber
  • SBS styrene-butadiene-styrene rubber
  • Styrene-isoprene-styrene rubber SIS
  • SEBS styrene-ethylene-butylene-styrene rubber
  • SIBS styrene-isobutylene-styrene block rubber
  • SIBS styrene-isoprene-propylene-styrene rubber
  • Styrene elastomers such as butyl rubber, polyisobutylene rubber, polybutene, polyisoprene rubber, nitrile butadiene rubber (NBR), etc., such as chloroprene rubber Vinyl chloride elastomer, such as chlorosulfonated polyethylene rubber, e.g., natural rubber.
  • the rubber contained in the resin foam is preferably an olefin elastomer, and more preferably EPDM.
  • EPDM is a rubber obtained by copolymerization of ethylene, propylene and dienes. In addition to ethylene and propylene, dienes are further copolymerized to introduce unsaturated bonds and enable crosslinking with a crosslinking agent. It is said.
  • dienes examples include 5-ethylidene-2-norbornene, 1,4-hexadiene, dicyclopentadiene, and the like. These dienes can be used alone or in combination of two or more.
  • the degree of crosslinking can be improved.
  • EPDM preferably, EPDM having long chain branching is mentioned.
  • the method for introducing a long branched chain into EPDM is not particularly limited, and a known method is employed.
  • a catalyst such as a Ziegler-Natta catalyst or a metallocene catalyst, and preferably with a metallocene catalyst from the viewpoint of obtaining a long branched chain.
  • the content (diene content) of dienes in EPDM is, for example, 1% by mass or more, preferably 2% by mass or more, more preferably 3% by mass or more, and particularly preferably 5% by mass or more. Moreover, for example, it is 20 mass% or less, Preferably, it is 15 mass% or less, More preferably, it is 10 mass% or less. If the diene content is less than this, the surface shrinkage of the EPDM foam obtained by foaming EPDM may occur, and the compression load may increase. Moreover, when more than this, a crack may arise in an EPDM foam.
  • foaming agents examples include organic foaming agents and inorganic foaming agents.
  • organic foaming agent examples include azo foaming agents such as azodicarboxylic amide (ADCA), barium azodicarboxylate, azobisisobutyronitrile (AIBN), azocyclohexylnitrile, azodiaminobenzene, and the like.
  • azo foaming agents such as azodicarboxylic amide (ADCA), barium azodicarboxylate, azobisisobutyronitrile (AIBN), azocyclohexylnitrile, azodiaminobenzene, and the like.
  • N-nitroso blowing agents such as N, N'-dinitrosopentamethylenetetramine (DTP), N, N'-dimethyl-N, N'-dinitrosoterephthalamide, trinitrosotrimethyltriamine, for example, 4,4'- Oxybis (benzenesulfonylhydrazide) (OBSH), paratoluenesulfonyl hydrazide, diphenylsulfone-3,3'-disulfonylhydrazide, 2,4-toluenedisulfonylhydrazide, p, p-bis (benzenesulfonylhydrazide) ether, benzene- 1,3-disul Hydrazide-based blowing agents such as phonylhydrazide and allylbis (sulfonylhydrazide), for example, p-toluylenesulfonyl semicarbazide, semicarbazide-based
  • Examples of the organic foaming agent include thermally expandable fine particles in which a heat-expandable substance is enclosed in a microcapsule.
  • thermally expandable particles include microspheres (trade name, Matsumoto). And commercial products such as those manufactured by Yushi Corporation.
  • the inorganic foaming agent examples include hydrogen carbonates such as sodium hydrogen carbonate and ammonium hydrogen carbonate, for example, carbonates such as sodium carbonate and ammonium carbonate, for example, nitrites such as sodium nitrite and ammonium nitrite, for example hydrogen.
  • hydrogen carbonates such as sodium hydrogen carbonate and ammonium hydrogen carbonate
  • carbonates such as sodium carbonate and ammonium carbonate
  • nitrites such as sodium nitrite and ammonium nitrite
  • hydrogen examples include borohydride salts such as sodium borohydride, for example, azides, and other known inorganic foaming agents. These foaming agents may be used alone or in combination of two or more.
  • an organic foaming agent is used, and more preferably, an azo foaming agent is used.
  • the blending ratio of the foaming agent is, for example, 0.1 parts by mass or more, preferably 1 part by mass or more, more preferably 10 parts by mass or more, and, for example, 50 parts by mass with respect to 100 parts by mass of rubber. Hereinafter, it is preferably 30 parts by mass or less.
  • crosslinking agents can be used alone or in combination of two or more.
  • crosslinking agent examples include quinoid compounds, organic peroxides, sulfur (S 8 ) and sulfur compounds, selenium, magnesium oxide, lead monoxide, polyamines, nitroso compounds, formaldehyde resins, ammonium salts, and the like.
  • a quinoid compound an organic peroxide, etc. are mentioned.
  • the quinoid compound is an organic compound having a quinoid structure (quinoid crosslinking agent), and examples thereof include p-quinonedioxime, poly-p-dinitrosobenzene, and derivatives thereof.
  • p-quinonedioxime derivatives include p, p′-dibenzoylquinonedioxime.
  • the quinoid compound is preferably a derivative of p-quinone dioxime, more preferably p, p′-dibenzoylquinone dioxime.
  • the rubber composition is cross-linked by the p-quinonedioxime derivative, so that the content of sulfur atoms can be reduced and the corrosivity is reduced. , Excellent foamability can be ensured.
  • the blending ratio of the quinoid compound is, for example, 0.05 parts by mass or more, preferably 0.5 parts by mass or more with respect to 100 parts by mass of rubber. 30 parts by mass or less, preferably 20 parts by mass or less, more preferably 10 parts by mass or less, and still more preferably 5 parts by mass or less.
  • the blending ratio of the p-quinonedioxime derivative is, for example, 0.05 parts by mass or more, preferably 0. 5 parts by mass or more, more preferably 1.5 parts by mass or more, and 20 parts by mass or less, preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and further preferably 3 parts by mass or less. But there is.
  • Organic peroxide is an organic compound having a peroxide structure (organic peroxide crosslinking agent).
  • dicumyl peroxide dimethyldi (t-butylperoxy) hexane, 1,1-di (t-butylperoxy) cyclohexane, ⁇ , ⁇ '-di (t-butylperoxy) diisopropylbenzene, etc. Is mentioned.
  • organic peroxides can be used alone or in combination of two or more.
  • the blending ratio of the organic peroxide is, for example, 0.05 parts by mass or more, preferably 0.5 parts by mass or more, with respect to 100 parts by mass of the rubber.
  • it is 1 part by mass or more, and for example, 20 parts by mass or less, preferably 15 parts by mass or less, more preferably 10 parts by mass or less, still more preferably 5 parts by mass or less, and particularly preferably 2 parts by mass. It is also below mass parts.
  • the crosslinking agent can be used alone or in combination of two or more.
  • a quinoid compound and an organic peroxide are used in combination as a crosslinking agent.
  • the mixing ratio of the organic peroxide is, for example, 1 part by mass or more, preferably 10 parts by mass or more with respect to 100 parts by mass of the quinoid compound. Yes, for example, 100 parts by mass or less, preferably 50 parts by mass or less.
  • the rubber composition preferably contains a foaming aid and a crosslinking aid.
  • foaming aids examples include urea foaming aids, salicylic acid foaming aids, benzoic acid foaming aids, and metal oxides (eg, zinc oxide).
  • urea foaming aids e.g, salicylic acid foaming aids
  • benzoic acid foaming aids e.g., benzoic acid foaming aids
  • metal oxides e.g, zinc oxide
  • urea-based foaming aids and metal oxides are used. These foaming aids may be used alone or in combination of two or more.
  • the blending ratio of the foaming aid is, for example, 0.5 parts by mass or more, preferably 1 part by mass or more, and for example, 20 parts by mass or less, preferably 10 parts by mass with respect to 100 parts by mass of rubber. It is as follows.
  • crosslinking aid examples include thiazoles (eg, dibenzothiazyl disulfide, 2-mercaptobenzothiazole), thioureas (eg, diethylthiourea, trimethylthiourea, dibutylthiourea), dithiocarbamic acids (eg, dimethyldithiocarbamic acid).
  • thiazoles eg, dibenzothiazyl disulfide, 2-mercaptobenzothiazole
  • thioureas eg, diethylthiourea, trimethylthiourea, dibutylthiourea
  • dithiocarbamic acids eg, dimethyldithiocarbamic acid
  • guanidines eg, diphenylguanidine, di-o-tolylguanidine, etc.
  • sulfenamides eg, benzothiazyl
  • thiurams eg tetramethylthiu Mumonosulfide, tetramethylthiuram disulfide, tetrabenzylthiuram disulfide, etc.
  • xanthates eg, sodium isopropylxanthate, zinc isopropylxanthate
  • aldehyde ammonia eg, acetaldehyde ammonia, hexam
  • examples of the crosslinking aid include alcohols.
  • examples of alcohols include monohydric alcohols such as ethanol, dihydric alcohols such as ethylene glycol, trihydric alcohols such as glycerin, polyols such as polyethylene glycol and polypropylene glycol (polyoxyethylene glycol), and the like. It is done.
  • a polyol is preferable.
  • the number average molecular weight of a polyol is 200 or more, for example, Preferably, it is 300 or more, for example, is 10,000 or less, Preferably, it is 5000 or less.
  • crosslinking aids can be used alone or in combination of two or more.
  • crosslinking aid alcohols are preferable, and polyols are more preferable.
  • the crosslinking aid is preferably a polyol, more preferably a polyoxyalkylene glycol, and still more preferably polyethylene. Glycol is used.
  • the rubber composition can be cross-linked satisfactorily, reducing corrosiveness and excellent foamability, and reducing the compression load. it can.
  • the blending ratio of the crosslinking aid is, for example, 0.01 parts by mass or more, preferably 0.02 parts by mass or more, more preferably 0.06 parts by mass or more, relative to 100 parts by mass of rubber. For example, it is 20 parts by mass or less, preferably 10 parts by mass or less, more preferably 5 parts by mass or less, more preferably 2 parts by mass or less.
  • the compounding ratio of the crosslinking aid is, for example, 200 parts by mass or less, preferably 100 parts by mass or less, more preferably 50 parts by mass or less with respect to 100 parts by mass of the crosslinking agent. It is also not less than 10 parts by mass, preferably not less than 10 parts by mass, more preferably not less than 20 parts by mass. In particular, with respect to 100 parts by mass of the quinoid compound, for example, 300 parts by mass or less, preferably 100 parts by mass or less, 50 parts by mass or less, and for example, 1 part by mass or more, preferably 15 parts by mass or more, More preferably, it is 25 parts by mass or more.
  • the rubber composition can appropriately contain a lubricant (processing aid), a pigment, a filler, a flame retardant, a softening agent and the like as necessary.
  • the lubricant examples include stearic acid and esters thereof, stearic compounds such as zinc stearate, and paraffin. These lubricants may be used alone or in combination of two or more.
  • the blending ratio of the lubricant is, for example, 0.1 parts by mass or more, preferably 1 part by mass or more, and for example, 20 parts by mass or less, preferably 10 parts by mass or less with respect to 100 parts by mass of rubber. It is.
  • the pigment examples include carbon black. These pigments may be used alone or in combination of two or more.
  • the blending ratio of the pigment is, for example, 1 part by mass or more, preferably 2 parts by mass or more, and for example, 50 parts by mass or less, preferably 30 parts by mass or less with respect to 100 parts by mass of the rubber.
  • the filler examples include inorganic fillers such as calcium carbonate, magnesium carbonate, silicic acid and salts thereof, clay, talc, mica powder, bentonite, silica, alumina, aluminum silicate, aluminum powder, and organic materials such as cork. System fillers and other known fillers. These fillers may be used alone or in combination of two or more.
  • the blending ratio of the filler is, for example, 10 parts by mass or more, preferably 30 parts by mass or more, more preferably 50 parts by mass or more, and for example, 300 parts by mass or less, relative to 100 parts by mass of rubber. Preferably, it is 200 mass parts or less.
  • the flame retardant examples include hydroxides such as calcium hydroxide, magnesium hydroxide, and aluminum hydroxide. These flame retardants may be used alone or in combination of two or more.
  • the blending ratio of the flame retardant is, for example, 5 parts by mass or more, preferably 10 parts by mass or more, more preferably 15 parts by mass or more, for example, 200 parts by mass or less, preferably 100 parts by mass of rubber. 150 parts by mass or less, more preferably 100 parts by mass or less.
  • the softener examples include petroleum oils (for example, paraffinic process oil (such as paraffin oil), naphthenic process oil, drying oils and animal and vegetable oils (such as linseed oil), aroma-based process oil, etc.) , Asphalts, low molecular weight polymers, organic acid esters (eg, phthalate esters (eg, di-2-ethylhexyl phthalate (DOP), dibutyl phthalate (DBP)), phosphate esters, higher fatty acid esters, alkyls Sulfonic acid esters, etc.) and thickeners.
  • organic acid esters eg, phthalate esters (eg, di-2-ethylhexyl phthalate (DOP), dibutyl phthalate (DBP)
  • phosphate esters eg, higher fatty acid esters, alkyls Sulfonic acid esters, etc.
  • These softeners may be used alone or in combination of two or more.
  • the rubber composition is used, for example, as a plasticizer, an anti-aging agent, an antioxidant, a colorant, an antifungal agent, in a range that does not affect the excellent effect of the obtained resin foam depending on its purpose and use.
  • Known additives such as non-rubber polymers can be appropriately contained.
  • the pressure-sensitive adhesive composition forming the pressure-sensitive adhesive layer contains, for example, synthetic rubber.
  • Examples of the synthetic rubber include thermoplastic elastomers and thermosetting elastomers.
  • thermoplastic elastomer olefin-based elastomers such as ethylene-propylene rubber (EPM) and ethylene-propylene-diene rubber (EPDM) such as styrene-butadiene rubber (SBR), styrene-butadiene-styrene rubber (SBS), Styrene-isoprene-styrene rubber (SIS), styrene-ethylene-butadiene rubber, styrene-ethylene-butylene-styrene rubber (SEBS), styrene-isobutylene-styrene block rubber (SIBS), styrene-isoprene-propylene-styrene rubber, etc.
  • EPM ethylene-propylene rubber
  • EPDM ethylene-propylene-diene rubber
  • SBR styrene-butadiene rubber
  • SBS Styrene-isoprene-st
  • Styrenic elastomers such as butyl rubber, polyisobutylene rubber, polybutene, polyisoprene rubber, nitrile butadiene rubber (NBR) and other butyl elastomers such as chloroprene Rubber, vinyl chloride elastomer, such as chlorosulfonated polyethylene rubber.
  • thermosetting elastomers examples include silicone rubber, fluorine rubber, acrylic rubber, and polyamide rubber.
  • thermoplastic elastomers more preferred are styrene elastomers and butyl elastomers, and still more preferred are polyisobutylene and SIBS.
  • the weight average molecular weight of the synthetic rubber is, for example, 30,000 or more, preferably 50,000 or more, more preferably 100,000 or more, and for example, 5 million or less, preferably 3 million or less, more preferably 1 million or less. Within this range, the pressure-sensitive adhesive layer can sufficiently exhibit adhesive strength.
  • the weight average molecular weight is measured in terms of polystyrene using gel permeation chromatography.
  • the pressure-sensitive adhesive composition preferably contains a peeling aid.
  • the peeling aid examples include oligomers.
  • the pressure-sensitive adhesive layer can have an appropriate adhesive strength, and the water-stopping property, temporary fixing property, low contamination property, etc. of the foamed laminate are further improved.
  • the number average molecular weight of the oligomer is, for example, 300 or more, preferably 500 or more, for example, 10,000 or less, preferably 7000 or less.
  • the number average molecular weight is measured in terms of polystyrene using gel permeation chromatography.
  • oligomer examples include a compound having a polyoxyalkylene unit, a polyolefin, and an acrylic oligomer.
  • Examples of the compound having a polyoxyalkylene unit include polyoxypropylene glyceryl ether and polyoxyethylene polyoxypropylene block polymer.
  • compounds containing phosphorus such as polyoxyethylene stearyl ether phosphoric acid are also included.
  • polystyrene examples include polypropylene and polyethylene.
  • the acrylic oligomer is a copolymer obtained by polymerization of a monomer containing (meth) acrylic acid alkyl ester.
  • the (meth) acrylic acid alkyl ester is a methacrylic acid alkyl ester and / or an acrylic acid alkyl ester.
  • methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, (meth) Examples include hexyl acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate and the like, and linear or branched (meth) acrylic acid alkyl esters having an alkyl moiety of 1 to 10 carbon atoms are preferable. Includes a linear or branched alkyl (meth) acrylate having an alkyl moiety of 2 to 8 carbon atoms.
  • a (meth) acrylic acid alkyl ester having two or more alkyl groups is used in combination. More specifically, combined use of an acrylic acid alkyl ester having an alkyl moiety of 2 to 6 carbon atoms (particularly 2 to 4) and an acid alkyl ester having an alkyl moiety of 7 to 12 carbon atoms (particularly 7 to 8 carbon atoms). Is mentioned.
  • the content of the alkyl alkyl acrylate ester having 7 to 12 carbon atoms relative to 100 parts by mass of the alkyl alkyl acrylate ester having 2 to 6 carbon atoms is, for example, preferably 1 part by mass or more. Is 10 parts by mass or more, more preferably 100 parts by mass or more, and for example, 500 parts by mass or less, preferably 300 parts by mass or less.
  • the oligomer preferably includes a compound having a polyoxyalkylene unit.
  • a peeling aid By containing such a peeling aid, the adhesive strength of the pressure-sensitive adhesive layer can be in a favorable range, and the foamed laminate can be sufficiently temporarily attached to the member to be sealed, and after sealing It is possible to reduce contamination. Moreover, the water-stopping property can be improved.
  • the content of the peeling aid is, for example, 0.1 parts by mass or more, preferably 0.5 parts by mass or more, and for example, 20 parts by mass or less, preferably 100 parts by mass of the synthetic rubber. 15 parts by mass or less, more preferably 10 parts by mass or less.
  • the pressure-sensitive adhesive layer may contain other additives as necessary within a range not impairing the effects of the present invention.
  • the pressure-sensitive adhesive layer preferably does not contain a crosslinking agent that crosslinks a peeling aid such as an oligomer.
  • the production method of the foam laminate 1 includes, for example, a foam layer preparation step for preparing (manufacturing) the foam layer (resin foam) 2, an undercoat step for forming the undercoat layer 3 on one surface of the foam layer 2, and a release substrate 5.
  • An adhesive layer laminated substrate 6 formed by laminating an adhesive layer 4 and a foaming layer 2 on which an undercoat layer 3 is disposed, and an adhesive layer laminated substrate 6 (adhesive layer 4 side).
  • the foamed layer 2 (undercoat layer 3 side) and a peeling step of peeling the release substrate 5 from the foamed laminate 1.
  • the foam layer preparation step a known or commercially available foam is prepared.
  • the foaming layer which is a rubber-type foam can also be prepared by making a rubber composition foam.
  • kneading can be performed while heating appropriately.
  • components other than the cross-linking agent, the cross-linking aid, the foaming agent and the foaming aid are first kneaded to prepare the primary mixture, and then the cross-linking agent and the cross-linking aid are added to the primary mixture.
  • a rubber composition (secondary mixture) can also be prepared by adding an agent, a foaming agent and a foaming aid and kneading.
  • a part of crosslinking adjuvant can also be mix
  • the prepared rubber composition (mixture) is extruded into a sheet or the like using an extruder (molding process), and the extruded rubber composition is heated and foamed (foaming process).
  • the foam composition is appropriately selected depending on the crosslinking start temperature of the blended crosslinking agent, the foaming temperature of the blended foaming agent, and the like.
  • a hot air circulation oven for example, 40 to 200 ° C.
  • After preheating at 60 to 160 ° C. for example, 1 to 60 minutes, preferably 5 to 40 minutes, for example, 450 ° C. or less, preferably 100 to 350 ° C., more preferably 120 to 250 It is heated at, for example, 5 to 80 minutes, preferably 15 to 50 minutes.
  • a resin foam rubber-based foam
  • a resin foam that can suppress the corrosion of the member and can seal the member with good adhesion and step following ability is easily and efficiently produced. be able to.
  • the prepared rubber composition can be extruded into a sheet shape (molding process) while heating using an extruder, and the rubber composition can be continuously crosslinked and foamed (foaming process).
  • the rubber composition is crosslinked while being foamed, and a foamed layer (rubber foam) 2 can be obtained (FIG. 1A).
  • the thickness of the foamed layer 2 is, for example, 0.1 mm or more, preferably 1 mm or more, more preferably 5 mm or more, and for example, 50 mm or less, preferably 45 mm or less, more preferably 30 mm or less. .
  • the foamed layer 2 has an open cell structure (open cell rate of 100%) or a semi-open semi-closed cell structure (open cell rate of more than 0% and less than 100%, preferably open cell rate of 50 to 95%). If the foamed layer 2 is an open-cell structure or a semi-continuous semi-closed cell structure, the flexibility can be improved, and consequently the sealing property of the resin foam between the members can be improved.
  • the cell diameter of the foamed layer 2 is, for example, 50 ⁇ m or more, preferably 100 ⁇ m or more, more preferably 200 ⁇ m or more, for example, 1200 ⁇ m or less, preferably 1000 ⁇ m or less, more preferably 800 ⁇ m or less.
  • the volume expansion ratio (density ratio before and after foaming) of the foam layer 2 is, for example, 2 times or more, preferably 5 times or more, and usually 30 times or less.
  • an undercoat layer 3 is formed on one surface (upper surface) of the foam layer 2 (undercoat step).
  • the undercoat layer 3 is formed, for example, by applying and drying an undercoat liquid on the surface of the foamed layer 2 by a known method such as an applicator.
  • the undercoat liquid is obtained, for example, by dissolving or dispersing rubber in a solvent.
  • Such rubber includes natural rubber and synthetic rubber.
  • Examples of the synthetic rubber include the same ones as described above.
  • Preferred examples include polyisobutylene, polybutene, polyisoprene, and the like, and more preferred is the combined use of polyisobutylene and polybutene.
  • the content of polybutene is, for example, 10 parts by mass or more, preferably 50 parts by mass or more with respect to 100 parts by mass of polyisobutylene, and for example, 200 parts by mass. Hereinafter, it is preferably 150 parts by mass or less.
  • the rubber used in the undercoat liquid is preferably a rubber having a weight average molecular weight of, for example, 10,000 or more, preferably 20,000 or more, and, for example, 200,000 or less, preferably 100,000 or less. It is done. Alternatively, a rubber having a number average molecular weight of, for example, 500 or more, preferably 1000 or more, and 5000 or less, preferably 3000 or less is mentioned. In particular, when a rubber having an average molecular weight in the above range is used in combination, the foam layer 2 and the pressure-sensitive adhesive layer 4 can be more reliably fixed.
  • the solvent examples include water, for example, ketones such as acetone and methyl ethyl ketone (MEK), aromatic hydrocarbons such as toluene, xylene, and ethylbenzene, esters such as ethyl acetate, and the like such as N, N-dimethylformamide. And amides.
  • ketones such as acetone and methyl ethyl ketone (MEK)
  • aromatic hydrocarbons such as toluene, xylene, and ethylbenzene
  • esters such as ethyl acetate, and the like such as N, N-dimethylformamide.
  • amides examples of the solvent include water, for example, ketones such as acetone and methyl ethyl ketone (MEK), aromatic hydrocarbons such as toluene, xylene, and ethylbenzene, esters such as ethyl acetate, and the like such
  • the undercoat liquid may contain other known additives.
  • the solid content in the undercoat liquid is, for example, 10% by mass or more, preferably 20% by mass or more, for example, 90% by mass or less, preferably 80% by mass or less.
  • the drying temperature is, for example, 60 ° C. or more, preferably 70 ° C. or more, and for example, 150 ° C. or less, preferably 120 ° C. or less.
  • the drying time is, for example, 10 seconds or more, preferably 30 seconds or more, and for example, 30 minutes or less, preferably 10 minutes or less.
  • the thickness of the undercoat layer 3 thus obtained is, for example, 3 ⁇ m or more, preferably 5 ⁇ m or more, and for example, 100 ⁇ m or less, preferably 50 ⁇ m or less.
  • the pressure-sensitive adhesive layer laminated substrate 6 and the foamed layer 2 are disposed to face each other (arrangement step). Then, as shown to FIG. 1D, the adhesive layer laminated base material 6 is laminated
  • an adhesive layer laminated substrate 6 in which the adhesive layer 4 is laminated on one surface of the release substrate 5 is prepared.
  • the pressure-sensitive adhesive layer laminated substrate 6 is obtained by applying and drying a pressure-sensitive adhesive solution containing a pressure-sensitive adhesive composition and a solvent on one surface of the release substrate 5 by a known method such as an applicator.
  • Examples of the solvent include the same solvents as those described above for the undercoat liquid.
  • the solid content in the pressure-sensitive adhesive solution is, for example, 3% by mass or more, preferably 5% by mass or more, for example, 95% by mass or less, preferably 90% by mass or less.
  • peeling substrate 5 examples include a polyethylene terephthalate (PET) film, a polyethylene film, a polypropylene film, and paper. These are subjected to mold release treatment on the surface with, for example, a fluorine release agent, a long-chain alkyl acrylate release agent, a silicone release agent, or the like.
  • PET polyethylene terephthalate
  • a fluorine release agent for example, a fluorine release agent, a long-chain alkyl acrylate release agent, a silicone release agent, or the like.
  • the drying temperature is, for example, 60 ° C. or more, preferably 70 ° C. or more, and for example, 150 ° C. or less, preferably 120 ° C. or less.
  • the drying time is, for example, 10 seconds or more, preferably 30 seconds or more, and for example, 30 minutes or less, preferably 10 minutes or less.
  • the thickness of the pressure-sensitive adhesive layer 4 thus obtained is, for example, 1 ⁇ m or more, preferably 5 ⁇ m or more, more preferably 10 ⁇ m or more, and for example, 100 ⁇ m or less, preferably 50 ⁇ m or less, more preferably 30 ⁇ m or less.
  • the shear storage elastic modulus in 25 degreeC of the adhesive layer 4 is 1.5 * 10 ⁇ 5 > Pa or more, Preferably, it is 2.0 * 10 ⁇ 5 > Pa or more, More preferably, it is 2.5 * 10 ⁇ 5 > Pa. That's it. Moreover, for example, it is 7.0 ⁇ 10 5 Pa or less, preferably 6.0 ⁇ 10 5 Pa or less, and more preferably 5.0 ⁇ 10 5 Pa or less.
  • the shear storage elastic modulus When the shear storage elastic modulus is within the above range, the waterproof property of the foamed laminate is good. Moreover, temporary fixing to a member becomes easy.
  • the pressure-sensitive adhesive layer laminated substrate 6 and the foam layer 2 are arranged so that the pressure-sensitive adhesive layer 4 and the undercoat layer 3 face each other with a gap (FIG. 1C).
  • the pressure-sensitive adhesive layer laminated substrate 6 is laminated on the foamed layer 2 (lamination step). Specifically, the pressure-sensitive adhesive layer 4 and the undercoat layer 3 are brought into contact with each other.
  • the pressure-sensitive adhesive layer laminated substrate 6 and / or the foamed layer 2 are pressed and heated as necessary.
  • peeling substrate 5 is peeled from the foamed laminate 1 (peeling step). That is, the peeling base material 5 is peeled off from the surface of the pressure-sensitive adhesive layer 4 as indicated by arrows and phantom lines in FIG. 1D.
  • the total thickness of the foamed laminate 1 thus obtained is, for example, 1 mm or more, preferably 3 mm or more, and for example, 50 mm or less, preferably 30 mm or less.
  • the apparent density (according to JIS K 6767 (1999)) of the foamed laminate 1 is, for example, 0.50 g / cm 3 or less, preferably 0.2 g / cm 3 or less, usually 0.01 g / cm 3 or more. It is. According to such a foam laminate 1, excellent foamability can be ensured, and the member can be satisfactorily sealed.
  • the content ratio of the sulfur atom in the foamed laminate 1 is 1000 ppm or less, preferably 800 ppm or less, more preferably 500 ppm or less on a mass basis.
  • the sulfur atom content ratio is within the above range, the corrosion of the member to be sealed can be reliably reduced by the sulfur contained in the foamed laminate 1.
  • the sulfur atom content is calculated based on the measurement result of the fluorescent X-ray measurement using an XRF apparatus (ZXS100e, manufactured by Rigaku).
  • Content of the foam laminate 1 in the sulfur S 8 for example, 100 ppm or less, preferably 50 ppm or less, more preferably 10ppm or less.
  • the content ratio of sulfur S 8 can be measured by gel permeation gas chromatography (GPC).
  • the 50% compression load value (according to JIS K 6767 (1999)) of the foam laminate 1 is 0.40 N / cm 2 or less, 0.30 N / cm 2 or less, more preferably 0.25 N / cm. 2 or less, more preferably 0.20 N / cm 2 or less.
  • it is 0.05 N / cm 2 or more, preferably 0.10 N / cm 2 or more, more preferably 0.15 N / cm 2 or more.
  • the 50% compression load value exceeds the above upper limit, an excessive load is required when compressing and sealing the foam laminate to the member.
  • the adhesive layer of the foam laminate adheres firmly to the member. Therefore, when the foamed laminate is peeled off, the pressure-sensitive adhesive layer remains on the member, and the member is contaminated. Moreover, since an excessive load is applied to the member, the member may be deformed or broken.
  • the tensile strength of the foamed laminate 1 (maximum load in a tensile test according to JIS K 6767 (1999)) is, for example, 1.0 N / cm 2 or more and 2.0 N / cm 2 or more. 0 N / cm 2 or less, preferably 30.0 N / cm 2 or less.
  • the elongation percentage (according to JIS K 6767 (1999)) of the foam laminate 1 is, for example, 10% or more, preferably 150% or more, and, for example, 1500% or less, preferably 1000%. It is as follows.
  • the adhesive strength with respect to the acrylic plate on the pressure-sensitive adhesive layer 4 side is, for example, 0.05 N / 25 mm or more, preferably 0.4 N in the initial stage (that is, when contacting the adherend for the first time after the foamed laminate 1 is manufactured).
  • / 25 mm or more more preferably 1.0 N / 25 mm or more, more preferably 3.0 N / 25 mm or more, for example, 4.0 N / 25 mm or less, preferably 3.5 N / 25 mm or less.
  • the measuring method of adhesive force is mentioned later in an Example. When the adhesive strength is within the above range, temporary fixing can be further ensured, and the contamination is excellent.
  • the foam laminate 1 has a compressibility at which water can stop after 24 hours in the U-shaped water-stopping test is 60% or less, preferably 55% or less, more preferably 50% or less. % Or more.
  • the measuring method of the U-shaped water-stopping test will be described later in Examples.
  • the compression ratio is within the above range, the water-stopping property of the foamed laminate is good and water leakage can be suppressed. Moreover, the contamination to the member after peeling a foaming laminated body can be suppressed.
  • the compressibility (water-adhesion after peeling) after 24 hours in the re-U-shaped water-stopping test is 60% or less, preferably 55% or less, more preferably 50% or less. For example, it is 5% or more. If the compression rate at this time is within the above range, it is possible to further seal (rework) after peeling the foam laminate, and the foam laminate can be reused.
  • the measuring method of the re-U-shaped water-stopping test will be described later in Examples.
  • this foaming laminated body 1 is equipped with the foaming layer 2 formed from a resin foam, and the adhesive layer 4 laminated
  • the shear storage elastic modulus in 25 degreeC of an adhesive layer However, it is 1.5 ⁇ 10 5 Pa or more. Therefore, since the pressure-sensitive adhesive layer has a fine tack, it can be temporarily fixed to the member.
  • a 50% compressive load is 0.40 N / cm ⁇ 2 > or less, and the compressibility which can stop water 24 hours after in a U-shaped water-stopping test is 60% or less. Therefore, it is excellent in water stop. Furthermore, since water can be stopped with a low compressive load, when the member and the foamed laminate are peeled off after sealing, a part of the foamed laminate is prevented from leaving glue remaining on the member, and the low contamination property is excellent. Therefore, there is no need for removal of adhesive residue from the member, and the workability is excellent.
  • the pressure-sensitive adhesive layer contains a synthetic rubber
  • the water-stopping property can be more reliably improved and the temporary fixing can be more reliably performed.
  • the water-stopping property is further improved.
  • the foamed laminate 1 is not particularly limited, and seals gaps of various members for the purpose of vibration suppression, sound absorption, sound insulation, dust prevention, heat insulation, buffering, water tightness, etc., for example, vibration insulation, sound absorption material, sound insulation It can be used as a material, a dustproof material, a heat insulating material, a buffer material, a waterstop material, and the like. More specifically, it is used for a gap between a car casing and a part (for example, a taillight), a gap between an electric / electric equipment casing and a part (for example, an engine control unit (ECU)), and the like. it can.
  • ECU engine control unit
  • an undercoat layer 3 is laminated on one surface of the foam layer 2, and an adhesive layer 4 is laminated on the surface of the undercoat layer 3.
  • the pressure-sensitive adhesive layer 4 can be directly laminated on the foam layer 2 without laminating the undercoat layer 3 on the layer 2.
  • the undercoat layer 3 is preferably provided on the foam layer 2.
  • the peeling substrate 5 is peeled from the pressure-sensitive adhesive layer 4, but if necessary, the peeling substrate 5 may be used until actually used. Can also be laminated.
  • the pressure-sensitive adhesive layer 4 is formed only on one surface of the foam layer 2.
  • the pressure-sensitive adhesive layer 4 is formed on one surface and the other surface of the foam layer 2.
  • the pressure-sensitive adhesive layer 4 can be formed on one surface of the foam layer 2, and a commercially available or known double-sided adhesive tape can be formed on the other surface of the foam layer 2.
  • the rubber composition was extruded into a sheet having a thickness of about 8 mm using a single screw extruder (45 mm ⁇ ) to produce a rubber composition sheet.
  • the rubber composition sheet was preheated at 140 ° C. for 20 minutes in a hot air circulation oven. Thereafter, the temperature was raised to 170 ° C. in a hot-air circulation oven over 10 minutes, and the rubber composition sheet was heated at 170 ° C. for 10 minutes to be foamed to obtain a foamed layer (EPDM foam).
  • the thickness was 30 mm.
  • the prepared undercoat liquid was applied to one side of the EPDM obtained in Production Example 1 with an applicator, and the undercoat liquid was dried at 80 ° C. for 3 minutes, and an undercoat layer (thickness 15 ⁇ m) was formed on one side of the EPDM foam. ) Was formed.
  • Example 1 In the compounding quantity as described in the compounding prescription shown in Table 1, each component was mix
  • This adhesive solution is applied to the surface of a release substrate (“MRF # 38”, manufactured by Mitsubishi Plastics) with an applicator and heated at 80 ° C. for 2 minutes to form an adhesive layer having a thickness of 15 ⁇ m.
  • a pressure-sensitive adhesive layer-forming substrate was produced.
  • the pressure-sensitive adhesive layer side of the obtained pressure-sensitive adhesive layer-forming substrate was brought into contact with the surface of the EPDM foam undercoat layer obtained in Example 3, and then the release substrate was peeled from the pressure-sensitive adhesive layer. Thereby, the foaming laminated body of Example 1 was manufactured.
  • Examples 2 to 8 Except having changed the compounding prescription of an adhesive layer into the compounding prescription shown in Table 2, it carried out similarly to Example 1, and manufactured the foaming layered product of each example.
  • XRF equipment Rigaku ZXS100e
  • X-ray source Vertical Rh tube Analysis area: 30mm ⁇
  • Analytical element range B to U Further, the quantification was calculated based on the ratio of sulfur element in all the detected elements.
  • the THF solution was filtered through a 0.45 ⁇ m membrane filter, and the filtrate was subjected to gel permeation chromatography.
  • the filtrate was diluted to a predetermined concentration to prepare a standard solution, this standard solution was subjected to gel permeation chromatography measurement, and a calibration curve was created from the obtained peak area value.
  • the pressure-sensitive adhesive layer surface of the sample for evaluation was attached to an acrylic plate (manufactured by Mitsubishi Rayon Co., Ltd., trade name: Acrylite L) by reciprocating 2 kg rollers. After curing at 23 ° C. for 30 minutes, the adhesive strength was measured using a universal tensile tester (manufactured by Minebea Co., Ltd., product name: TCM-1kNB) at a peeling angle of 180 degrees and a pulling speed of 10 m / min.
  • a universal tensile tester manufactured by Minebea Co., Ltd., product name: TCM-1kNB
  • the adhesive strength is, for example, 0.05 to 4 N / 25 mm, it is considered suitable for temporary fixing.
  • Shear storage elastic modulus G ′ in the pressure-sensitive adhesive layer of the foam laminate (10 mm) was measured using a dynamic viscoelasticity measuring device (“ARES”, manufactured by TA Instruments) under the following measurement conditions. Based on.
  • Torsion mode Measurement temperature range: -70 ° C to 150 ° C Temperature increase rate: 5 ° C / min Measurement frequency: 1Hz H) Water-stop test (initial) Test by pasting a double-sided tape (acrylic double-sided tape, manufactured by Nitto Denko Corporation) on the foamed layer side of the foamed laminate (10 mm), and then punching it into a U-shape (foamed laminate width 10 mm, total length 300 mm) A piece was made. Next, the test piece was sandwiched between the acrylic plate and the stainless steel plate from the thickness direction of the test piece so that the open end of the test piece (the open end in the U-shape) was directed upward.
  • a double-sided tape acrylic double-sided tape, manufactured by Nitto Denko Corporation
  • the pressure-sensitive adhesive layer was in contact with the acrylic plate and the double-sided tape was in contact with the stainless steel plate.
  • the acrylic plate and the stainless steel plate were pressed in the thickness direction of the test piece so that the test piece was compressed by 10% in thickness.
  • ADCA Azodicarbonamide AC # LQ, foaming agent, urea-based compound made by Eiwa Kasei Kogyo Co., Ltd .: Cell paste K5, foaming aid, made by Eiwa Kasei Kogyo Co., Ltd.
  • Zinc oxide 2 types of zinc oxide, foaming aid, Mitsui Metal Mining Sulfur: Alpha Gran S-50EN, cross-linking agent, Tochi Co., p, p'-dibenzoylquinone dioxime: Barnock DGM, cross-linking agent, Ouchi Shinsei Chemical Co., Ltd., ⁇ , ⁇ '-di (t-butyl Peroxy) diisopropylbenzene: perbutyl P-40MB, 1 minute half-life temperature: 175 ° C, crosslinking agent, NOF polyethylene glycol: PEG4000S, number average molecular weight 3400, crosslinking aid, Sanyo Chemical Industries 2-mercaptobenzo Thiazole: Noxeller M, crosslinking aid, N, N'-dibutylthiourea manufactured by Ouchi Shinsei Chemical Co., Ltd .: Noxeller BUR, crosslinking aid, Ouchi Shinsei Zinc Dibenzyldithiocarbamate: Noxeller
  • Stearic acid Powdered stearic acid sakura, lubricant, NOF Corporation Paraffin: Parapere 130, Lubricant, Taniguchi Oil Co., Ltd.
  • Carbon black Asahi # 50, pigment, Asahi Carbon Co.
  • the foam laminate of the present invention can be suitably used as a sealing material for various industrial products, and in particular, used for vibration-proof materials, sound-absorbing materials, sound-insulating materials, dust-proof materials, heat-insulating materials, shock-absorbing materials, water-stopping materials, etc. Can do.

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  • Health & Medical Sciences (AREA)
  • Organic Chemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Polymers & Plastics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Emergency Medicine (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Laminated Bodies (AREA)
  • Sealing Material Composition (AREA)

Abstract

L'invention concerne une mousse stratifiée qui comprend : une couche alvéolaire qui est formée d'une mousse de résine ; et une couche adhésive qui est stratifiée sur au moins une surface de la couche alvéolaire. La couche adhésive possède un module de conservation en cisaillement à 25°C de 1,5 × 105 Pa ou plus. Cette mousse stratifiée possède une charge de compression à 50 % de 0,40 N/cm2 ou moins, et le taux de compression associé auquel l'eau peut être arrêtée après 24 heures dans un test d'arrêt d'eau en forme de U est de 60 % ou moins.
PCT/JP2014/056201 2013-03-19 2014-03-10 Mousse stratifiée WO2014148297A1 (fr)

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WO2017002957A1 (fr) * 2015-07-02 2017-01-05 日東電工株式会社 Mousse de caoutchouc d'éthylène-propylène-diène, et matériau d'étanchéité
JP6755133B2 (ja) * 2015-07-02 2020-09-16 日東電工株式会社 エチレン・プロピレン・ジエンゴム発泡体、その製造方法およびシール材
WO2017002958A1 (fr) * 2015-07-02 2017-01-05 日東電工株式会社 Mousse de caoutchouc d'éthylène-propylène-diène, procédé pour sa fabrication et matériau d'étanchéité
JP6757609B2 (ja) * 2015-07-02 2020-09-23 日東電工株式会社 エチレン・プロピレン・ジエンゴム発泡体およびシール材
JP7186045B2 (ja) * 2018-09-26 2022-12-08 マクセル株式会社 防音材
JP7160667B2 (ja) * 2018-12-27 2022-10-25 マクセル株式会社 防音材

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